E-mail: humski@nana.pharma.hr
Summary: a) Cyclopropylmethyl and cyclobutyl derivatives solvolyze
by way of very complicated structures. We expect that by monitoring the
percentage of internal rearrangements in various solvents to gain
information of factors that influence the formation of the intimate ion
pair, as well as its conversion to products. b) The single evidence that
squalenyl chloride solvolyze with extended pi-paricipation is the secondary
kinetic deuterium isotope effect. In order to support the existence of
extended pi-participation we intend to prepare and solvolyze related
supstrates with differently substituted phenyl groups, and calculate the
rho,sigma-correlations.

Research goals: a) The aim of investigation is to establish the
influence of nucleofilicity and ionization power of the solvent on the
carbocation (internal ion pair) reactivity in solvolysis of
cyclopropylmethyl (cyclobutyl) derivatives. These results may be important
for understanding the structure of intermediates in these reactions, as
well as for understanding the reactivity of internal ion pairs in general.
b) In nature the squalene derivative cyclization leads to steroid hormones,
but the mechanism is still unknown. In previous papers we demonstrated
using deuterium kinetic isotope effects that squalenyl chloride in
biomimetic conditions solvolyzes by way of extended pi-participation. Since
it is the single proof of the mechanim, we also intend to prove it using
rho,sigma- correlations.